Methods to produce fuels

Abstract

The present disclosure generally relates to the catalytic conversion of alcohols into hydrocarbon ketones suitable for use as fuels. More specifically, the present disclosure relates to the catalytic conversion of a mixture of isopropanol-butanol-ethanol (IBE) or acetone-butanol-ethanol (ABE), into ketones suitable for use as fuels. The ABE or IBE mixtures may be obtained from the fermentation of biomass or sugars.

The invention claimed is: 
     
       1. A method of producing a mixture of hydrocarbon ketones, comprising contacting acetone and at least two or more primary alcohols with catalyst and optionally base to produce a mixture of hydrocarbon ketones, wherein at least a portion of the mixture of hydrocarbon ketones is produced from double alkylation of the acetone, and
 wherein the catalyst comprises Pd, Cu, and hydrotalcite (HT). 
 
     
     
       2. The method of  claim 1 , wherein the Pd and Cu are coprecipitated or impregnated on the HT. 
     
     
       3. The method of  claim 1 , wherein the catalyst further comprises Ni, Zn, Ru, Co, or Pt, or any combination thereof. 
     
     
       4. The method of  claim 1 , wherein the catalyst further comprises zeolite. 
     
     
       5. A method of producing a mixture of hydrocarbon ketones, comprising contacting acetone and at least two or more primary alcohols with catalyst and optionally base to produce a mixture of hydrocarbon ketones, wherein at least a portion of the mixture of hydrocarbon ketones is produces from doubly alkylation of the acetone, and
 wherein the catalyst comprises Pd—Cu/HT, Pd—Cu/HT-C, Pd—Cu/HT/C, Pd—Cu/NiHT, or PdCu/ZnHT, or any combinations thereof. 
 
     
     
       6. The method of  claim 1 , wherein at least 70% of the mixture of hydrocarbon ketones are produced from double alkylation of the acetone. 
     
     
       7. The method of  claim 1 , wherein the mixture of hydrocarbon ketones is a mixture of C 5-15  hydrocarbon ketones. 
     
     
       8. The method of  claim 1 , wherein the mixture of hydrocarbon ketones is selected from the group consisting of 2-pentanone, 4-heptanone,2-heptanone, 4-nonanone, 2-methyl-4-nonanone, 6-undecanone, 5-ethylundecan-6-one, 5,7-diethylundecan-6-one, 5,7-dibutylundecan-6-one, 9-ethyltridecan-6-one, 5,11-diethylpentadecan-8-one, 5-butylundecan-6-one, 5-butyl-7-ethylundecan-6-one, and any combinations thereof. 
     
     
       9. A method of producing a mixture of hydrocarbon ketones, comprising:
 a) contacting biomass or sugars with a fermentation host to produce a fermentation product mixture, wherein the fermentation product mixture comprises acetone, butanol and ethanol; 
 b) isolating at least a portion of the acetone, butanol and ethanol from the fermentation product mixture; and 
 c) contacting the isolated acetone, butanol and ethanol with metal catalyst and optionally base to produce a mixture of hydrocarbon ketones, wherein at least 20% of the mixture of hydrocarbon ketones are C 7+  hydrocarbon ketones and wherein at least a portion of the mixture of hydrocarbon ketones is produced from doubly alkylation of the acetone, and 
 wherein the catalyst comprises Pd, Cu, and hydrotalcite (HT). 
 
     
     
       10. The method of  claim 1 , wherein at least 70% of the mixture of hydrocarbon ketones is C 7+  hydrocarbon ketones. 
     
     
       11. The method of  claim 1 , wherein the base is selected from the group consisting of K 3 PO 4 , KOH, Ba(OH) 2 .8H 2 O, K 2 CO 3 , KOAc, KH 2 PO 4 , Na 2 HPO 4 , pyridine, Et 3 N, and any combinations thereof. 
     
     
       12. The method of  claim 1 , wherein the metal catalyst further comprises TiO 2 , zeolite, or a combination thereof. 
     
     
       13. The method of  claim 1 , wherein the catalyst comprises:
 Pd—Cu/HT; 
 Pd—Cu/HT/C; 
 Pd—Cu/HT and zeolite; 
 Pd—Cu/HT/C and zeolite; 
 Pd—Cu/HT and TiO 2 ; 
 Pd—Cu/HT-C and TiO 2 ; 
 Pd—Cu/HT/C and TiO 2 ; 
 Pd—Cu/C and HT; 
 Pd—Cu/HT-C; 
 Pd—Cu/NiHT; 
 Pd—Cu/ZnHT; 
 Cu/SiO 2 , Pd/C and HT/C; 
 Cu/SiO 2 , Pd/C and HT; 
 Cu/ZnO/Al 2 O 3 , Pd/C and HT; or 
 Pd—Cu/ZnO/HT. 
 
     
     
       14. The method of  claim 1 , wherein the HT is coprecipitated or impregnated on carbon to form a support, and the Pd and Cu are coprecipitated or impregnated on the support. 
     
     
       15. The method of  claim 1 , wherein the HT is mixed with carbon to form a support, and the Pd and Cu are coprecipitated or impregnated on the support. 
     
     
       16. The method of  claim 1 , wherein at least 40% of the mixture of hydrocarbon ketones is C 11+  hydrocarbon ketones.